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Groundwater provides much of the world's potable water. Nevertheless, groundwater quality monitoring programmes often rely on a sporadic, slow, and narrowly focused combination of periodic manual sampling and laboratory analyses, such that some water quality deficiencies go undetected, or are detected too late to prevent adverse consequences. In an effort to address this shortcoming, we conducted enhanced monitoring of untreated groundwater quality over 12 months (February 2019-February 2020) in four shallow wells supplying potable water in Finland. We supplemented periodic manual sampling and laboratory analyses with (i) real-time online monitoring of physicochemical and hydrological parameters, (ii) analysis of stable water isotopes from groundwater and nearby surface waters, and (iii) microbial community analysis of groundwater via amplicon sequencing of the 16S rRNA gene and 16S rRNA. We also developed an early warning system (EWS) for detecting water quality anomalies by automating real-time online monitoring data collection, transfer, and analysis - using electrical conductivity (EC) and turbidity as indirect water quality indicators. Real-time online monitoring measurements were largely in fair agreement with periodic manual measurements, demonstrating their usefulness for monitoring water quality; and the findings of conventional monitoring, stable water isotopes, and microbial community analysis revealed indications of surface water intrusion and faecal contamination at some of the studied sites. With further advances in technology and affordability expected into the future, the supplementary methods used here could be more widely implemented to enhance groundwater quality monitoring - by contributing new insights and/or corroborating the findings of conventional analyses.

Mining operations produce large quantities of wastewater. At a mine site in Northern Finland, two natural peatlands are used for the treatment of mining‐influenced waters with high concentrations of sulfate and potentially toxic arsenic (As). In the present study, As removal and the involved microbial processes in those treatment peatlands (TPs) were assessed. Arsenic‐metabolizing microorganisms were abundant in peat soil from both TPs (up to 108 cells gdw‐1), with arsenate respirers being about 100 times more abundant than arsenite oxidizers. In uninhibited microcosm incubations, supplemented arsenite was oxidized under oxic conditions and supplemented arsenate was reduced under anoxic conditions, while little to no oxidation/reduction was observed in NaN3‐inhibited microcosms, indicating high As‐turnover potential of peat microbes. Formation of thioarsenates was observed in anoxic microcosms. Sequencing of the functional genemarkers aioA (arsenite oxidizers), arrA (arsenate respirers), and arsC (detoxifying arsenate reducers) demonstrated high diversity of the As‐metabolizing microbial community. The microbial community composition differed between the two TPs, which may have affected As removal efficiencies. In the present situation, arsenate reduction is likely the dominant net process and contributes substantially to As removal. Changes in TP usage (e.g. mine closure) with lowered water tables and heightened oxygen availability in peat might lead to reoxidation and remobilization of bound arsenite. peerReviewed

Highlights • Peatland microbes catalyze oxidation and reduction of arsenic and antimony species. • Microbial As/Sb reduction is crucial for efficient contaminant removal in peatlands. • Temperature strongly affects microbial arsenic and antimony turnover rates. • Removal in winter possible due to low concentrations and long water residence times. Arsenic (As) and antimony (Sb) from mining-affected waters are efficiently removed in two treatment peatlands (TPs) in Northern Finland. However, the exact mechanisms behind this removal are not well resolved. Thus, the present study combines results from microcosm experiments and pilot-scale TPs on the effects of microbes, temperature, and carbon substrate to elucidate the role of peat microorganisms in As and Sb removal. The main As and Sb species in TP inflow water are arsenate and antimonate. In peat microcosms, they were quantitatively reduced, however, at rates about 20–400 times lower than previously reported from pure cultures, likely due to excess of other terminal electron acceptors, such as nitrate and sulfate. Addition of the microbial inhibitor sodium azide inhibited reduction, indicating that it is indeed microbially mediated. Arsenite and antimonite (re)oxidation, which is in situ likely limited to upper, oxic peat layers, was likewise observed in peat microcosms. Only for antimonite, oxidation also occurred abiotically, likely catalyzed by humic acids or metals. Process rates increased with increasing temperature, but all processes occurred also at low temperatures. Monitoring of pilot-scale TPs revealed only minor effects of winter conditions (i.e., low temperature and freezing) on arsenic and antimony removal. Formation of methylated oxyarsenates was observed to increase As mobility at the onset of freezing. From different carbon substrates tested, lactate slightly enhanced arsenate reduction and antimonate reduction was stimulated by acetate, lactate, and formate. However, a maximum rate enhancement of only 1.8 times indicates that carbon substrate availability is not the rate-limiting factor in microbial arsenate or antimonate reduction. The collective data indicate that microorganisms catalyze reduction and (re)oxidation of As and Sb species in the TPs, and even though temperature is a major factor controlling microbial As and Sb reduction/(re)oxidation, low inflow concentrations, long water residence times, and the presence of unfrozen peat in lower layers allow for efficient removal also under winter conditions.

The HYDRUS wetland module is widely used together with the biokinetic model CWM1 to simulate reactive transport of contaminants in constructed wetlands. However, this approach has not been used previously to simulate processes in peat-based wetlands operating in cold climates and treating mining-influenced water. In this study, the goal was to clarify changes in flow, transport, and nitrogen removal processes in cold climate treatment peatlands by assessing the performance of HYDRUS-CWM1. Flow and non-reactive transport of tracer, and reactive transport of ammonium, nitrite, and nitrate, in two pilot wetlands operated under controlled conditions representing frozen (winter) and frost-free (summer) periods were simulated. Model simulation outputs were compared against data obtained from the pilot wetlands and from a full-scale treatment peatland treating mining-influenced water in an Arctic region. Initial peaks in tracer concentration were simulated satisfactorily, but transformation and transport of nitrogen species in treatment peatlands, especially under partially frozen conditions, were modeled with only limited success. Limitations of the model and the assumptions made for the simulations have been discussed to highlight the challenges in modeling of treatment peatlands. Highlights • Initial peaks in tracer concentration were simulated satisfactorily. • Transport of nitrogen especially in winter was modeled with limited success. • Limitations of the model and possibilities for improvement are discussed. • Possibility to use multiple HYDRUS add-ons simultaneously may be critical.

Treatment peatlands are water purification systems located on existing mires. They are commonly used to treat different types of waters, ranging from municipal wastewaters to mine effluent. This study evaluated the capacity of unmanned aerial vehicle (UAV)-based thermal infrared (TIR) imaging, color infrared imaging, and stable water isotopes as a combined method for monitoring the functioning of a treatment peatland purifying mine process effluent water under boreal conditions in northern Finland. The results showed that TIR was an efficient tool for pinpointing cold groundwater seepage points in the peatland area that were not otherwise visible. Color infrared imaging was used to define Normalized Difference Vegetation Index (NDVI), as an indicator of plant health in the treatment area. A NDVI map of the area, measured on a day representing the main growing season (summer, +12 °C day temperature), revealed areas with stressed coniferous trees. This was probably due to excess water in these areas, resulting from successful spread of the process effluent water to the treatment peatland. Stable water isotopes were able to spatially differentiate the treated process effluent water, surface waters, and groundwater in different parts of the treatment peatland. This first attempt at combining these methods in monitoring of treatment peatlands was promising, as the results obtained with different methods complemented each other. While they produce only a snapshot of prevailing conditions, all three methods, singly and in combination, could be valuable tools in treatment peatland management.

Nitrogen (N) loads from municipal and mine wastewater discharges typically increase N concentrations in recipient water bodies which should get more attention especially in cold-climate regions. This study compared N removal efficiency of six constructed wetlands (CWs) treating mine waters and three CWs polishing municipal wastewater. There were clear impacts of point source N loading to recipient water bodies in all cases studied and >300-fold increase in N was seen in some cases. First-order N removal coefficient was determined for seven of these CWs. All CWs studied were observed to remove N efficiently during the warm growing season but the amount of N released increased significantly during the cold season. Although some year-round purification was achieved by both peat-based and pond-type CWs, removal of nitrate + nitrite-N ((NO3− + NO2−)-N) was low during winter. The first-order N removal coefficient varied from 4.9 · 10−6 to 1.9 · 10−3 d−1 and showed that peat-based CWs were slightly more efficient in N removal than pond-type CWs. However, purification efficiency was steadier and higher for pond-type CWs, as lower hydraulic load or longer water residence time compensated for purification performance. Pond-type CWs showed mean removal efficiency of 59% and 46% for ammonium-N (NH4+-N) and (NO3− + NO2−)-N, respectively, whereas peatland-type CWs had lower removal efficiency for NH4+-N (mean of 26%) and in many cases negative removal for (NO3− + NO2−)-N. Correlation analysis revealed no clear, systematic relationship between temperature and N removal. However, in some CWs the highest correlation was between temperature and (NO3− + NO2−)-N, reflecting lower denitrification rate at lower temperature. More than 50% removal was found to require a hydraulic load below 10 mm d−1. In order to achieve 70% of NH4+-N removal, Ntot load lower than 75 g m−2 year−1 and a residence time longer than 80 d are needed in CWs in cold-climate regions.

Increased metal mining in the Arctic region has caused elevated loads of arsenic (As), antimony (Sb), nickel (Ni), and sulfate (SO42-) to recipient surface or groundwater systems. The need for cost-effective active and passive mine water treatment methods has also increased. Natural peatlands are commonly used as a final step for treatment of mining influenced water. However, their permanent retention of harmful substances is affected by influent concentrations and environmental conditions. The effects of dilution, pH, temperature, oxygen availability, and contaminant accumulation on retention and leaching of As, Sb, Ni, and sulfate from mine process water and drainage water obtained from treatment peatlands in Finnish Lapland were studied in batch sorption experiments, and discussed in context of field data and environmental impacts. The results, while demonstrating effectiveness of peat to remove the target contaminants from mine water, revealed the risk of leaching of As, Sb, and SO42- from treatment peatlands when diluted mine water was introduced. Sb was more readily leached compared to As while leaching of both was supported by higher pH of 9. No straightforward effect of temperature and oxygen availability in controlling removal and leaching was evident from the results. The results also showed that contaminant accumulation in treatment peatlands after long-term use can lead to decreased removal and escalated leaching of contaminants, with the effect being more pronounced for As and Ni.

Arsenic contamination in water by natural causes or industrial activities is a major environmental concern, and treatment of contaminated waters is needed to protect water resources and minimize the risk for human health. In mining environments, treatment peatlands are used in the polishing phase of water treatment to remove arsenic (among other contaminants), and peat microorganisms play a crucial role in arsenic removal. The present study assessed culture-independent diversity obtained through metagenomic and metatranscriptomic sequencing and culture-dependent diversity obtained by isolating psychrotolerant arsenic-tolerant, arsenite-oxidizing, and arsenate-respiring microorganisms from a peatland treating mine effluent waters of a gold mine in Finnish Lapland using a dilution-to-extinction technique. Low diversity enrichments obtained after several transfers were dominated by the genera Pseudomonas, Polaromonas, Aeromonas, Brevundimonas, Ancylobacter, and Rhodoferax. Even though maximal growth and physiological activity (i.e., arsenite oxidation or arsenate reduction) were observed at temperatures between 20 and 28°C, most enrichments also showed substantial growth/activity at 2–5°C, indicating the successful enrichments of psychrotolerant microorganisms. After additional purification, eight arsenic-tolerant, five arsenite-oxidizing, and three arsenate-respiring strains were obtained in pure culture and identified as Pseudomonas, Rhodococcus, Microbacterium, and Cadophora. Some of the enriched and isolated genera are not known to metabolize arsenic, and valuable insights on arsenic turnover pathways may be gained by their further characterization. Comparison with phylogenetic and functional data from the metagenome indicated that the enriched and isolated strains did not belong to the most abundant genera, indicating that culture-dependent and -independent methods capture different fractions of the microbial community involved in arsenic turnover. Rare biosphere microorganisms that are present in low abundance often play an important role in ecosystem functioning, and the enriched/isolated strains might thus contribute substantially to arsenic turnover in the treatment peatland. Psychrotolerant pure cultures of arsenic-metabolizing microorganisms from peatlands are needed to close the knowledge gaps pertaining to microbial arsenic turnover in peatlands located in cold climate regions, and the isolates and enrichments obtained in this study are a good starting point to establish model systems. Improved understanding of their metabolism could moreover lead to their use in biotechnological applications intended for bioremediation of arsenic-contaminated waters.

Seasonally frozen ground (SFG) occurs on ~25% of the Northern Hemisphere’s land surface, and the influence of SFG on water, energy, and solute fluxes is important in cold climate regions. The hydrological role of permafrost is now being actively researched, but the influence of SFG has been receiving less attention. Intuitively, water movement in frozen ground is blocked by ice forming in soil pores that were open to water flow prior to freezing. However, it has been shown that the hydrological influence of SFG is insignificant in some cases, with soil remaining permeable to water even when frozen. There is a clear knowledge gap concerning (1) how intensively and (2) under what physiographical and climate conditions SFG influences hydrological fluxes. We conducted a systematic literature review examining the hydrological importance of SFG we found reported in 143 publications. We found a clear hydrological influence of frozen ground in small-scale laboratory measurements, but a more ambiguous effect when the spatial scale under study increased to hillslopes, catchments, or watersheds. We also found that SFG may be hydrologically less important in forested areas or in regions with deep snow cover. Our systematic review suggests that hydrological influence of SFG may become more important in a future warmer climate with less snow and intensified land use in high-latitude areas.

Impacts of mining on water quality are a great concern in the Arctic region. This study evaluated the impact of pre-treated mine effluent on river water quality. The study was conducted along the Seurujoki River in sub-Arctic Finland, which is impacted by Kittila gold mine. The study analyzed water quality and hydrological data upstream and downstream of the mining area over an eight-year period, including a tailing dam leakage event in 2015. The analysis focused on water quality determinants such as electrical conductivity (EC), sulfate, antimony, manganese, and total nitrogen (Ntotal). Descriptive statistics on river water at four stations along the river corridor showed negative impacts of mining activities on the recipient water body. In order to find an indicator for water quality, correlation analysis between the water quality determinants was carried out. It identified EC as a good indicator for continuous water quality monitoring, especially to detect mining accidents such as partial failure of a tailings dam. The results showed increasing contaminant concentrations due to mining as more mine effluent was generated over time. A linear mixed model was developed to predict the coefficient of different elements affecting EC at river water monitoring stations impacted by mining effluents. The results provide new information on how to assess mining water impacts and plan future water quality monitoring.

Northern peatlands in their natural state are sinks of carbon dioxide (CO2) but sources of methane (CH4). They are often nitrogen limited and can act as sinks for greenhouse gas (GHG) nitrous oxide (N2O). Peatlands have been used to treat wastewaters from different point sources. Continuous nutrient and pollutant load to a nutrient limited peatland ecosystem may change the microbial processes and lead to increased productivity, which together are likely to change the GHG emissions. We studied the effect of wastewater derived from metal mining on N2O and CH4 emissions on two treatment peatlands in northern boreal zone. The measured CH4 fluxes from the reference point without any wastewater load were in the range of those reported from northern pristine peatlands while emissions from treatment peatlands were greatly reduced, presumably as result of high sulfate concentration in the porewater. N2O emissions were small in the reference point, but up to 300 times higher in the treatment peatlands. Methane emissions increased with increasing total organic carbon concentration and decreased with increasing sulfate concentration in the surface water, respectively, while N2O emissions increased with increasing nitrate concentrations. The data indicate drastic changes in GHG fluxes and related biogeochemical processes in treatment peatlands as compared to the reference point.

Peatlands and other wetlands are sinks for antimony (Sb), and solid natural organic matter (NOM) may play an important role in controlling Sb binding. However, direct evidence of Sb sequestration in natural peat samples is lacking. Here, we analyzed solid phase Sb, iron (Fe), and sulfur (S) as well as aqueous Sb speciation in three profiles up to a depth of 80 cm in a mine water impacted peatland in northern Finland. Linear combination fittings of extended X-ray absorption fine structure spectra showed that Sb binding to Fe phases was of minor importance and observed only in the uppermost layers of the peatland. Instead, the dominant (to almost exclusive) sequestration mechanism was Sb(III) binding to oxygen-containing functional groups, and at greater depths, increasingly Sb(III) binding to thiol groups of NOM. Aqueous Sb speciation was dominated by antimonate, while antimonite concentrations were low, further supporting our findings of much higher reactivity of Sb(III) than Sb(V) toward peat surfaces. Insufficient residence time for efficient reduction of antimonate to antimonite currently hinders higher Sb removal in the studied peatland. Overall, our findings imply that Sb(III) binding to solid NOM acts as an important sequestration mechanism under reducing conditions in peatlands and other high-organic matter environments.

Peatlands, used for purification of mining waste waters, have shown efficient solid-phase sequestration of contaminants such as arsenic (As). However, contaminant re-mobilization may occur related to management changes or chemical alteration of original peatland conditions. For a treatment peatland in Finnish Lapland, we here confirm efficient As retention in near-surface peat layers close to the mining waste water inflow, likely due to binding to FeIII-phases. Seven years into operation of the treatment peatland, there appears to be further retention potential, as large areas downstream still had solid-phase As concentrations at background levels. However, via depth-resolved pore water analysis we observed a hotspot 170 m from the inflow at 10–50 cm depth, where As pore water concentrations exceeded input concentrations by a factor of 20, indicating substantial As re-mobilization. At the same spot, a peak of reduced sulfur (S) species was found. Arsenic species detected were arsenite and up to 26% methylated oxyarsenates, 15% methylated and 7.9% inorganic thioarsenates. We postulate that As mobilization is a result of short-term re-equilibration to a changed inflow chemistry after installation of a process water treatment plant and a long-term consequence of changing pore water pH from acidic to near-neutral, releasing reduced S and As. We infer that the co-occurrence of reduced S and As leads to formation of methylated and/or thiolated As species with known low sorption affinity, thereby further enhancing As mobility. Laboratory incubation studies with two peat cores confirmed a high S-induced As mobilization potential, especially when As-Fe-rich, oxic surface layers were incubated anoxically at near-neutral pH. Highest risk of As re-mobilization from this treatment peatland is expected in a scenario in which mining waste water inflow has stopped but the peatland remains flooded, and near-surface layers transition from oxic to anoxic conditions.

Aquaculture needs practical solutions for nutrient removal to achieve sustainable fish production. Passive denitrifying bioreactors may provide an ecological, low-cost and low-maintenance approach for wastewater nitrogen removal. However, innovative organic materials are needed to enhance nitrate removal from the low carbon effluents in intensive recirculating aquaculture systems (RAS). In this study, we tested three additional carbon sources, including biochar, dried Sphagnum sp. moss and industrial potato residues, to enhance the performance of woodchip bioreactors treating the low carbon RAS wastewater. We assessed nitrate (NO3−) removal and microbial community composition during a one-year in situ column test with real aquaculture wastewater. We found no significant differences in the NO3− removal rates between the woodchip-only bioreactor and bioreactors with a zone of biochar or Sphagnum sp. moss (maximum removal rate 31–33 g NO3−-N m−3 d−1), but potato residues increased NO3− removal rate to 38 g NO3−-N m−3 d−1, with stable annual reduction efficiency of 93%. The readily available carbon released from potato residues increased NO3−-N removal capacity of the bioreactor even at higher inflow concentrations (>52 mg L−1). The microbial community and its predicted functional potential in the potato residue bioreactor differed markedly from those of the other bioreactors. Adding potato residues to woodchip material enabled smaller bioreactor size to be used for NO3− removal. This study introduced industrial potato by-product as an alternative carbon source for the woodchip denitrification process, and the encouraging results may pave the way toward growth of blue bioeconomy using the RAS.

Antimony (Sb) is a common contaminant in natural peatlands used as treatment wetlands for water influenced by metal mining in cold-climate regions. However, while other metalloids such as arsenic have been well studied, little is known about removal and retention of Sb in northern wetlands under challenging environmental conditions. In this study we assessed short-term, long-term and seasonal variations in mobility, removal, and retention of Sb from mining-influenced water in two peat based natural wetlands with different loading and physical conditions. Analyses based on 10 years of water quality data and data on contaminant accumulation in the peat soil revealed that the wetland with significantly lower hydraulic load and Sb areal load achieved adequate Sb removal, but with a slight decline in recent years. Antimony concentrations at the wetland outlet were slightly lower in summers than in winters. Dilution due to high rainfall during summer may be the likely reason for low outlet concentrations towards the end of summer. Outlet Sb concentrations were on the rise after inlet water quality was significantly improved through enhanced pre-treatment indicating mobilization of accumulated Sb. In comparison, the smaller wetland with higher hydraulic and Sb loading had very low Sb removal and a stronger decrease in Sb concentration through dilution due to snowmelt. The results highlight the challenges in Sb retention which should get more attention when treatment wetlands are designed for Sb rich waters such as mine waters and there are changes in water treatment arrangement in specific cases.

Peatlands are used for the purification of mining-affected waters in Northern Finland. In Northern climate, microorganisms in treatment peatlands (TPs) are affected by long and cold winters, but studies about those microorganisms are scarce. Thus, the bacterial, archaeal and fungal communities along gradients of mine water influence in two TPs were investigated. The TPs receive waters rich in contaminants, including arsenic (As), sulfate (SO42-) and nitrate (NO3-). Microbial diversity was high in both TPs, and microbial community composition differed between the studied TPs. Bacterial communities were dominated by Proteobacteria, Actinobacteria, Chloroflexi and Acidobacteria, archaeal communities were dominated by Methanomicrobia and the Candidate phylum Bathyarchaeota, and fungal communities were dominated by Ascomycota (Leotiomycetes, Dothideomycetes, Sordariomycetes). The functional potential of the bacterial and archaeal communities in TPs was predicted using PICRUSt. Sampling points affected by high concentrations of As showed higher relative abundance of predicted functions related to As resistance. Functions potentially involved in nitrogen and SO42- turnover in TPs were predicted for both TPs. The results obtained in this study indicate that (i) diverse microbial communities exist in Northern TPs, (ii) the functional potential of the peatland microorganisms is beneficial for contaminant removal in TPs and (iii) microorganisms in TPs are likely well-adapted to high contaminant concentrations as well as to the Northern climate.